WO2005113639A1 - Copolycarbonates a fluidite amelioree - Google Patents

Copolycarbonates a fluidite amelioree Download PDF

Info

Publication number
WO2005113639A1
WO2005113639A1 PCT/EP2005/004383 EP2005004383W WO2005113639A1 WO 2005113639 A1 WO2005113639 A1 WO 2005113639A1 EP 2005004383 W EP2005004383 W EP 2005004383W WO 2005113639 A1 WO2005113639 A1 WO 2005113639A1
Authority
WO
WIPO (PCT)
Prior art keywords
mol
copolycarbonates
bisphenol
formula
bisphenols
Prior art date
Application number
PCT/EP2005/004383
Other languages
German (de)
English (en)
Inventor
Helmut-Werner Heuer
Rolf Wehrmann
Michael Erkelenz
Alexander Meyer
Melanie MÖTHRATH
Original Assignee
Bayer Materialscience Ag
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayer Materialscience Ag filed Critical Bayer Materialscience Ag
Priority to EP05739541A priority Critical patent/EP1749043B1/fr
Priority to CN2005800224853A priority patent/CN1980978B/zh
Priority to JP2007511934A priority patent/JP2007536420A/ja
Publication of WO2005113639A1 publication Critical patent/WO2005113639A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/04—Aromatic polycarbonates
    • C08G64/06—Aromatic polycarbonates not containing aliphatic unsaturation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20—General preparatory processes
    • C08G64/30—General preparatory processes using carbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates

Definitions

  • the present invention relates to copolycarbonates with reduced water absorption and improved flowability, processes for their production and their use for the production of certain products, and the products obtainable therefrom.
  • Aromatic polycarbonates belong to the group of engineering thermoplastics. They are characterized by the combination of the technologically important properties of transparency, heat resistance and toughness.
  • the alkali salts of bisphenols are reacted with phosgene in a two-phase mixture.
  • the molecular weight can be determined by the amount of monophenols such as e.g. Phenol or tert-butylphenol can be controlled. These reactions almost exclusively produce linear polymers. This can be demonstrated by end group analysis.
  • branching agents as a rule multiply hydroxylated compounds, branched polycarbonates are also obtained.
  • the bisphenols are reacted with diaryl carbonates, usually diphenyl carbonate, in the presence of catalysts, such as alkali salts, ammonium or phosphonium compounds.
  • melt transesterification process is described, for example, in Encyclopedia of Polymer Science, Vol. 10 (1969), Chemistry and Physics of Polycarbonates, Polymer Reviews, H. Schnell, Vol. 9, John Wiley and Sons, Inc. (1964) and DE-C 1031 512.
  • R 1 and R 2 for hydrogen or linear or branched C 1 -C 4 alkyl, preferably for hydrogen or linear or branched C 1 -C 4 alkyl, particularly preferably for hydrogen or linear or branched C 1 -C 4 alkyl, very particularly preferably for hydrogen or Stand methyl and
  • X stands for O or S.
  • the present invention therefore relates to copolycarbonates containing at least two different bisphenols as monomers, a bisphenol being selected from at least one of the compounds of the formula (1),
  • R 1 and R 2 for hydrogen or linear or branched C 1 -C 6 alkyl, preferably for hydrogen or linear or branched C 1 -C 6 alkyl, particularly preferably for hydrogen or linear or branched C 1 -C 4 alkyl, very particularly preferably for hydrogen or Stand for methyl and stands for O or S.
  • the present invention furthermore relates to the bisphenols of the compounds of the formula (1), 0) in which
  • R 1 and R 2 for hydrogen or linear or branched C 1 -C 10 alkyl, preferably for hydrogen or linear or branched C 1 -C 6 alkyl, particularly preferably for hydrogen or linear or branched CC 4 alkyl, very particularly preferably for hydrogen or methyl stand and
  • X stands for O or S.
  • Particularly preferred compounds of the formula (1) are compounds of the formulas (Ia) and (Ib),
  • R 1 and R 2 have the meaning given above.
  • melt viscosity of the copolycarbonates obtained has lower values than the prior art, both at low and at higher shear rates (with an otherwise comparable molecular weight). This is particularly important for the production of larger injection molded parts, such as car windows. This makes it easier to fill the molds with common injection molding machines.
  • the diphenols of the formula (Ia) to be used according to the invention are known in the literature. The preparation of these substances is described for example in DE-A 22 37 762, DE-A 35 32 881, JP-A 2002 16 73 49 and JP-A 2003 16 05 26. The properties of this homopolycarbonate are described in H. Schnell, Chemistry and Physics of Polycarbonates, Polymer Reviews, Vol. 9, Interscience Publishers, New York 1964 p. 99 ff.
  • the 4,4'-hydroxy-substituted diphenyl ethers or diphenyl ether derivatives can be prepared by dimerizing hydroquinone or substituted hydroquinone derivatives.
  • the reactants in the presence of a catalyst such as e.g. reacted with an acidic ion exchanger.
  • a catalyst such as e.g. reacted with an acidic ion exchanger.
  • halogen-substituted phenols in a modified Ulimann reaction.
  • the reactants are exposed to copper salts such as CuCl reacted. In this way e.g. the meta-linked derivatives are also accessible.
  • the particularly preferred compounds are known (eg in A. Riemann, W. Ude, Ger. Offen. (1986), DE-A 3506845 or in Y. Kawamorita, M. Hisamura, Jpn. Kokai Tokkyo Koho (1988) , JP-A 63136051).
  • the prior art does not teach anything about improving the flowability of corresponding copolycarbonates.
  • the proportion of the bisphenols according to the invention in the copolycarbonate is generally 0.1-40 mol%, preferably 1-30 mol%, particularly preferably 5-25 mol% and very particularly preferably 10-20 mol%, based on the molar Amount of aromatic dihydroxy compounds used to make the copolycarbonates.
  • copolycarbonates prepared using the bisphenols of the formula (1) described and containing the structural units -O-D-O- derived from the compounds of the formulas 1 are exemplified, but not exclusively, by the general formula (2),
  • -E- independently of one another represent an aromatic radical having 6 to 40 C atoms, preferably 6 to 35 C atoms, particularly preferably 6 to 30 C atoms and very particularly preferably 6 to 25 C atoms, the one or more aromatic or may contain condensed aromatic nuclei, optionally containing heteroatoms, and preferably with C] -C ] 2 -alkyl radicals, preferably with C 1 -C 8 -alkyl radicals, particularly preferably with C 1 -C 4 -alkyl radicals and very particularly preferably with CC 6 - alkyl radicals or halogen Fluorine, chlorine or bromine, particularly preferably fluorine or chlorine, very particularly preferably fluorine, and may contain aliphatic radicals, cycloaliphatic radicals, aromatic nuclei or heteroatoms as bridge members
  • m stands for a fractional number z / k and n for a fractional number (k-z) / k where z stands for numbers from 1 to k.
  • Preferred diphenolate units of the branched copolycarbonates according to the invention are derived from general structures of the formula (3)
  • R and R independently of one another for H, linear or branched Ci-Cig-alkyl or alkoxy radicals, halogen such as Cl or Br or for an optionally substituted aryl or aralkyl radical, preferably for H or linear or branched C 1 -C 1 2-
  • alkyl particularly preferably H or Ci-Cg-alkyl radicals and very particularly preferably H or methyl
  • R 1 and R 2 represent linear or branched Ci-Cio-alkyl, preferably for linear C ⁇ -C ⁇ o-alkyl, particularly preferably for linear CC 8 alkyl and very particularly preferably for linear C ⁇ -C 6 alkyl and
  • X represents O or S
  • Y for a single bond, -SO 2 -, -CO-, a C to C 6 alkylene, C 2 - to C 5 - alkylidene, C 5 - to C 6 -cycloalkylidene radical, which is associated with C r to C 6 - Alkyl, preferably methyl or ethyl radicals can be substituted, or a C 6 to C 2 arylene radical,
  • p stands for a fractional number z / o and q stands for a fractional number (o-z) / o where z stands for numbers from 1 to o.
  • the diphenolate residues O-E-O in formula (2) and the diphenolate residues of the portion indicated by q as subscript in formula (3) are particularly preferably derived from the suitable diphenols mentioned below.
  • diphenols which, in addition to the bisphenols mentioned, are based on the general formulas (2) and (3), are hydroquinone, resorcinol, dihydroxybiphenyls, bis (hydroxyphenyl) alkanes, bis (hydroxyphenyl) cycloalkanes, bis ( hydroxyphenyl) sulf ⁇ de, bis (hydroxyphenyl) ether, bis (hydroxyphenyl) ketone, bis (hydroxyphenyl) sulfone, bis (hydroxyphenyl) sulfoxide, ⁇ , ⁇ '-bis (hydroxyphenyl) - diisopropylbenzenes, and their ring-alkylated and ring-halogenated compounds, and also called ⁇ , ⁇ -bis (hydroxyphenyl) polysiloxanes.
  • Preferred diphenols are, for example, 4,4'-dihydroxybiphenyl (DOD), 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), 1,1-bis (4-hydroxyphenyl) -3,3,5- trimethylcyclohexane
  • DOD 4,4'-dihydroxybiphenyl
  • bisphenol A 2,2-bis (4-hydroxyphenyl) propane
  • diphenols are, for example, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), 4,4'-dihydroxybiphenyl (DOD), 1,3-bis [2- (4-hydroxyphenyl) -2-propyl ] -benzene (bisphenol M), 2,2-bis- (3,5-dimethyI-4-hydroxyphenyI) -propane, l, l-bis- (4-hydroxyphenyI) -l-phenylethane, 2,2-bis- (3,5-dichloro-4-hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, l, l-bis (4-hydroxyphenyl) cyclohexane and l, l-bis- (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (bisphenol TMC).
  • bisphenol A 2,2-bis (4-hydroxyphenyl) propane
  • DOD 4,4'-dihydroxybiphenyl
  • 2,2-bis (4-hydroxyphenyl) propane bisphenol A
  • 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane bisphenol TMC
  • the diphenols can be used both alone and in a mixture with one another; both homopolycarbonates and copolycarbonates are included.
  • the diphenols are known from the literature or can be prepared by processes known from the literature (see, for example, H. J. Buysch et al., Ullmann's Encyclopedia of Industrial Chemistry, VCH, New York 1991, 5th Ed., Vol. 19, p. 348).
  • the polycarbonates or copolycarbonates can also be branched.
  • certain small amounts preferably amounts between 0.05 and 5 mol%, particularly preferably 0.1-3 mol%, very particularly preferably 0.1-2 mol%, based on the moles of diphenols used, of trifunctional compounds such as eg isatin biscresol (IBK) or phloroglucin, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -hepten-2; 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) heptane; 1,3,5-tri- (4-hydroxyphenyl) benzene; l, l, l-tri- (4-hydroxyphenyl) ethane (THPE); Tri- (4-hydroxyphenyl) phenylmethane; 2,2-bis [4,4-bis (4-hydroxyphenyl) -cyclohexyl] -propane; 2,4-bis (4-hydroxyphenyl-iso
  • Isatin biscresol and l, l, l-tri- (4-hydroxyphenyl) ethane and bis- (3-methyl-4-hydroxyphenyl) -2-oxo-2,3-dihydroindole are preferably used as branching agents.
  • the present invention further relates to a process for the preparation of the copolycarbonates of the formulas (2) and (3) according to the invention, characterized in that bisphenols and any branching agents are dissolved in aqueous alkaline solution and with a carbonate source such as phosgene, if appropriate, dissolved in a solvent a two-phase mixture of an aqueous alkaline solution, an organic solvent and a catalyst, preferably an amine compound, are reacted.
  • the reaction can also be carried out in several stages.
  • Such processes for the production of polycarbonate are basically two-phase interface processes e.g. from H. Schnell, Chemistry and Physics of Polycarbonates, Polymer Reviews, Vol. 9, Interscience Publishers, New York 1964 pp. 33 ff. and on Polymer Reviews, Vol. 10, "Condensation Polymers by Interfacial and Solution Methods", Paul W Morgan, Interscience Publishers, New York 1965, chap. VIJT, p. 325 known and therefore the basic conditions familiar to the expert.
  • the concentration of the bisphenols in the aqueous alkaline solution is 2 to 25% by weight, preferably 2 to 20% by weight, particularly preferably 2 to 18% by weight and very particularly preferably 3 to 15% by weight.
  • the aqueous alkaline solution consists of water in which hydroxides of alkali or alkaline earth metals are dissolved. Sodium and potassium hydroxides are preferred.
  • the volume ratio of aqueous alkaline solution to organic solvent is 5:95 to 95: 5, preferably 20:80 to 80:20, particularly preferably 30:70 to 70:30 and very particularly preferably 40:60 to 60 : 40th
  • the molar ratio of bisphenol to phosgene is less than 1:10, preferably less than 1: 6, particularly preferably less than 1: 4 and very particularly preferably less than 1: 3.
  • the concentration of the branched polycarbonates and copolycarbonates according to the invention in the organic phase is 1.0 to 25% by weight, preferably 2 to 20% by weight, particularly preferably 2 to 18% by weight and very particularly preferably 3 to 15% by weight. %.
  • the concentration of the amine compound based on the amount of bisphenol used is 0.1 to 10 mol%, preferably 0.2 to 8 mol%, particularly preferably 0.3 to 6 mol% and very particularly preferably 0.4 to 5 mol%.
  • Bisphenols are to be understood as the diphenols mentioned above, with proportions of the above-mentioned branching agents.
  • the carbonate source is phosgene, diphosgene or triphosgene, preferably phosgene. If phosgene is used, a solvent may be omitted and the phosgene may be introduced directly into the reaction mixture.
  • Tertiary amines such as triethylamine or N-alkylpiperidines can be used as the catalyst.
  • Trialkylamines and 4- (dimethylamino) pyridine are suitable as catalysts.
  • Triethylamine, tripropylamine, triisopropylamine, tributylamine, triisobutylamine, N-methylpiperidine, N-ethylpiperidine and N-propylpiperidine are particularly suitable.
  • Halogenated hydrocarbons such as methylene chloride and / or chlorobenzene, dichlorobenzene, trichlorobenzene or mixtures thereof or aromatic hydrocarbons such as e.g. Toluene or xylenes in question.
  • the reaction temperature can be -5 ° C. to 100 ° C., preferably 0 ° C. to 80 ° C., particularly preferably 10 ° C. to 70 ° C. and very particularly preferably 10 ° C. to 60 ° C.
  • the polycarbonates according to the invention can also be produced by the melt transesterification process.
  • the melt transesterification process is described, for example, in Encyclopedia of Polymer Science, Vol. 10 (1969), Chemistry and Physics of Polycarbonates, Polymer Reviews, H. Schnell, Vol. 9, John Wiley and Sons, Inc. (1964) and DE-C 1031 512.
  • R, R ! and R can independently represent H, C r C 34 alkyl or C 5 -C ⁇ 0 cycloalkyl, C 7 -C 34 alkaryl or C6-C 3 aryl, C ⁇ -C ⁇ 5 alkyl, C 5 - or C ⁇ -cycloalkyl,
  • H preferably independently of one another are H, CC 16 alkyl or C 5 -C 6 cycloalkyl, C 7 -C 6 alkaryl or C ⁇ -Ci ⁇ -aryl, R, R 'and R "H are particularly preferably.
  • Examples include:
  • the proportion of carbonic acid ester is 100 to 130 mol%, preferably 103 to 120 mol%, particularly preferably 103 to 109 mol%, based on the dihydroxy compound.
  • onium salts As catalysts in the context of the invention, basic catalysts such as, for example, alkali metal and alkaline earth metal hydroxides and oxides, but also ammonium or phosphonium salts, hereinafter referred to as onium salts, are used in the melt transesterification process as described in the literature mentioned. Onium salts are preferably used, particularly preferably phosphonium salts. Phosphonium salts for the purposes of the invention are those of the formula (6)
  • R 1 independently of one another for C r C ⁇ o-alkyl, C 6 -C ⁇ 0 aryl, C 7 -C ⁇ o aralkyl or C 5 -C 6 - cycloalkyl, preferably methyl or C 6 -C ⁇ 4 aryl, particularly preferably methyl or phenyl, and
  • X is an anion such as hydroxide, sulfate, hydrogen sulfate, hydrogen carbonate, carbonate, a halide, preferably chloride, or an alcoholate of the formula OR, where R is C ⁇ -Ci 4 aryl or C 7 -C] 2 aralkyl, preferably phenyl, can be.
  • Preferred catalysts are tetraphenylphosphonium chloride, tetraphenylphosphonium hydroxide, tetraphenylphosphoniumphenolate, particularly preferably tetraphenylphosphoniumphenolate.
  • the catalysts are preferably used in amounts of 10 "8 to 10 " 3 mol, particularly preferably 10 "7 to 10 " 4 mol, based on one mol of bisphenol.
  • Additional catalysts can be used alone or optionally in addition to the onium salt to increase the rate of polymerization.
  • These include salts of alkali metals and alkaline earth metals, such as hydroxides, alkoxides and aryl oxides of lithium, sodium and potassium, preferably hydroxide, alkoxide or aryl oxide salts of sodium. Most preferred are sodium hydroxide and sodium phenolate.
  • the amounts of the cocatalyst can range from 1 to 200 ppb, preferably 5 to 150 ppb and most preferably 10 to 125 ppb, each calculated as sodium.
  • the transesterification reaction of the aromatic dihydroxy compound and the carbonic acid diester in the melt is preferably carried out in two stages.
  • the aromatic dihydroxy compound and the carbonic acid diester are melted at temperatures of 80-250 ° C, preferably 100-230 ° C, particularly preferably 120-190 ° C under normal pressure in 0-5 hours, preferably 0.25- 3 hours instead.
  • the oligocarbonate is prepared from the aromatic dihydroxy compound and the carbonic acid diester by applying a vacuum (up to 2 mm Hg) and increasing the temperature (up to 260 ° C.) by distilling off the monophenol. The main amount of vapors falls out of the process on.
  • the oligocarbonate thus produced has an average weight molar mass M (determined by measuring the relative solution viscosity in dichloromethane or in mixtures of equal amounts by weight of phenol / o-dichlorobenzene calibrated by light scattering) in the range from 2000 g / mol to 18,000 g / mol, preferably of 4,000 g / mol to 15,000 g / mol.
  • the polycarbonate is produced in the polycondensation by further increasing the temperature to 250-320 ° C., preferably 270-295 ° C. and a pressure of ⁇ 2 mm Hg. This removes the rest of the vapors from the process.
  • the catalysts can also be used in combination (two or more) with one another.
  • alkali / alkaline earth metal catalysts When using alkali / alkaline earth metal catalysts, it may be advantageous to add the alkali / alkaline earth metal catalysts at a later point in time (for example after the oligocarbonate synthesis in the polycondensation in the second stage).
  • the reaction of the aromatic dihydroxy compound and the carbonic acid diester to form the polycarbonate can be carried out batchwise or preferably continuously in the sense of the process according to the invention, for example in stirred tanks, thin-film evaporators, falling film evaporators, stirred tank cascades, extruders, kneaders, simple disk reactors and high-viscosity disk reactors.
  • branched poly- or copolycarbonates can be produced by using multifunctional compounds.
  • the average molecular weights (Mw) of the branched polycarbonates and copolycarbonates according to the invention are in the range from 6,000 to 200,000 g / mol, preferably between 6,000 and 100,000 g / mol, particularly preferably between 10,000 and 80,000 g / mol and very particularly preferably between 12,000 and 70,000 g / mol (determined using GPC and polycarbonate calibration).
  • Preferred, particularly preferred or very particularly preferred are embodiments which make use of the parameters, compounds, definitions and explanations mentioned under preferred, particularly preferred or very particularly preferred or, preferably, etc.
  • copolycarbonates according to the invention can be worked up in a known manner and processed into any shaped articles, for example by extrusion, injection molding or extrusion blow molding.
  • aromatic polycarbonates and / or other aromatic polyester carbonates and / or other aromatic polyesters can be admixed to the copolycarbonates according to the invention in a known manner, for example by compounding.
  • thermoplastics such as fillers, UV stabilizers, thermal stabilizers, antistatic agents and pigments
  • additives customary for these thermoplastics can also be added to the polycarbonates and copolycarbonates according to the invention in the customary amounts; if necessary, the demolding behavior, the flow behavior and / or the flame resistance can be improved by adding external mold release agents, flow agents and / or flame retardants (eg alkyl and aryl phosphites, phosphates, phosphines, low molecular weight carboxylic acid esters, halogen compounds, salts, Chalk, quartz powder, glass and carbon fibers, pigments and their combinations, such compounds are described, for example, in WO 99/55772, pp. 15-25, and in the corresponding chapters of the "Plastics Additives Handbook", ed. 5 * Edition 2000, Hanser Publishers, Kunststoff.).
  • polycarbonates and copolycarbonates according to the invention can be processed into any shaped articles / extrudates used wherever known polycarbonates, polyester carbonates and polyesters are used. Due to their property profile, they are particularly suitable as materials for the injection molding of larger molded parts, for example car windows. Due to the low water absorption and the associated improved dimensional stability, they are also particularly suitable as substrate materials for optical data storage such as CD, CD-R, DVD, DVD-R, Blue-ray Disc or Advanced Optical Disc (AOD), but can also be used, for example, as foils in the electrical sector as molded parts in vehicle construction and as plates for covers in the security area. Further possible applications of the polycarbonates according to the invention are:
  • Safety panes which are known to be required in many areas of buildings, vehicles and aircraft, and as shields for helmets.
  • polycarbonates with a glass fiber content are used, which may additionally contain about 1-10% by weight of MoS 2 , based on the total weight.
  • optical device parts in particular lenses for photo and film cameras (see for example DE-A 2 701 173).
  • a light transmission carrier in particular as an optical fiber cable (see for example EP-A 0 089 801).
  • headlight lamps so-called “head-lamps”, flare lenses or inner lenses, and linear lights.
  • linear lights eg. B. headlight lamps, so-called “head-lamps”, flare lenses or inner lenses, and linear lights. 19.
  • oxygenators eg. dialyzers.
  • Safety glasses, visors or optical corrective glasses are provided.
  • the moldings and extrudates from the polymers according to the invention are also the subject of this application.
  • 126 ml of methylene chloride are added to a nitrogen-inertized solution of 8.088 g (0.04 mol) of 4,4'-dihydroxydiphenyl ether and 9.132 g (0.04 mol) of bisphenol A and 7.04 g (0.176 mol) of sodium hydroxide in 126 ml of water added.
  • 0.42 g (0.0028 mol or 3.5 mol% with respect to bisphenol) of p-tert-butylphenol (BÜP) is added as a chain terminator.
  • 11 ml (15.8 g, 0.16 mol) of phosgene are added over the course of 10 minutes.
  • 131 ml of methylene chloride are added to a solution of 0.809 g (0.004 mol) of 4,4'-dihydroxydiphenyl ether and 17.35 g (0.076 mol) of bisphenol A, which has been rendered inert with nitrogen, and 7.04 g (0.176 mol) of sodium hydroxide in 131 ml of water.
  • 0.36 g (0.0024 mol or 3.0 mol% with respect to bisphenol) of p-tert-butylphenol (BUP) is added as a chain terminator.
  • BUP p-tert-butylphenol
  • 11 ml (15.8 g, 0.16 mol) of phosgene are added over the course of 10 minutes.
  • 131 ml of methylene chloride are added to a nitrogen-inertized solution of 1.618 g (0.008 mol) of 4,4'-dihydroxy diphenyl ether and 16.438 g (0.072 mol) of bisphenol A and 7.04 g (0.176 mol) of sodium hydroxide in 131 ml of water.
  • 0.36 g (0.0024 mol or 3.0 mol% with respect to bisphenol) of p-tert-butylphenol (BUP) is added as a chain terminator.
  • BUP p-tert-butylphenol
  • 11 ml (15.8 g, 0.16 mol) of phosgene are added over the course of 10 minutes.
  • liquid crystalline behavior phase change from 200 ° C
  • IMVR describes the MVR with a heating-up time of 20 or 30 min compared to 6 min according to the ISO 1133 standard (designation IMVR 20 'or IMVR 30') as a limit value compared to the MVR according to ISO 1133.
  • Example 8 The copolycarbonate obtained in Example 8 is examined rheologically at 280 and 300 ° C. The following data is obtained:
  • Example 10 The copolycarbonate obtained in Example 10 is examined rheologically at 280 ° C. and 300 ° C. The following data is obtained: Viscosity [Pas]
  • the flow path for the Makrolon ® 2405 reference material was determined to be 30 cm and set as the standard.
  • melt viscosity is lower with approximately the same molecular weight.
  • copolycarbonates according to the invention from Examples 8 and 10 thus flow more easily than the comparative material Makrolon® 2605 based on bisphenol A.
  • This alkaline phase is acidified with 25% HCl solution and then extracted several times with diethyl ether.
  • the organic phase is washed several times with water and finally with saturated sodium chloride solution, dried over magnesium sulfate and filtered.
  • the solvent is removed in vacuo.
  • the dark brown, crystalline residue is recrystallized in chloroform with the addition of a mixture of activated carbon / tonsil. 24.4 g of a yellow solid with a melting point of 92 ° C. are obtained.
  • the mixture is allowed to cool and the residue is stirred up in 250 ml of semi-concentrated hydrochloric acid. It is extracted several times with toluene.
  • the combined organic phases are first washed with half-concentrated hydrochloric acid and then extracted several times with NaOH solution (10%).
  • the combined alkaline phases are re-extracted with a toluene / diethyl ether mixture (1: 1).
  • the solvent is removed in vacuo.
  • the crude product is over a silica gel column given (eluent: n-hexane / ethyl acetate 1: 1). After removing the solvent, the product is dried in vacuo and receives 26 g of a yellow oil.
  • the alkaline phase is acidified and then extracted several times with diethyl ether.
  • the organic phase is washed several times with water and finally with saturated sodium chloride solution, dried over magnesium sulfate, filtered and concentrated in vacuo.
  • the solvent is removed in vacuo and the product dried in vacuo. 13.0 g of a light-colored solid are obtained.
  • Example 22 corresponds to Example 22 except that the monomer from Example 19 was used instead of 3,3'-dihydroxydiphenyl ether.
  • Example 22 corresponds to Example 22, except that the monomer from Example 21 was used instead of 3,3'-dihydroxy diphenyl ether.
  • the zero viscosity is the intrinsic viscosity with a viscosity extrapolated to a zero shear rate.
  • the relative solution viscosity is determined dichloromethane at a concentration of 5 g / 1 at 25 ° C.
  • the phenolic OH content is obtained by IR measurement.
  • a difference measurement of a solution of 2 g of polymer in 50 ml of dichloromethane compared to pure dichloromethane is measured and the extinction difference at 3582 cm "'is determined.
  • the color number was determined as the difference in absorbance at 420 nm and 700 nm in dichloromethane at a concentration of 2.4 g / 50 ml and a layer thickness of 10 cm.
  • the apparatus is applied by applying a vacuum and rinsing freed of atmospheric oxygen with nitrogen (three times) and the mixture melted and the phenol formed was distilled off at 190 ° C.
  • a vacuum of 100 mbar was then applied and the mixture was distilled for a further 20 minutes
  • the vacuum is then set to 60 mbar within 5 minutes and held for 15 minutes, heated to 250 ° C. and held for 15 minutes, then the pressure is reduced to 5 mbar for 15 minutes, after which the temperature is raised to 280 ° C. heated again
  • the vacuum is reduced to 0.5 mbar over 15 minutes and stirred for a further 15 minutes.
  • the mixture is then heated to 300 ° C. and held for 30 minutes. Now the polycarbonate is drawn at normal pressure under a nitrogen atmosphere.

Abstract

La présente invention concerne des copolycarbonates présentant une meilleure fluidité, des procédés pour les produire, ainsi que leur utilisation pour produire des produits définis, les produits ainsi obtenus et de nouveaux bisphénols permettant de produire des polycarbonates.
PCT/EP2005/004383 2004-05-07 2005-04-23 Copolycarbonates a fluidite amelioree WO2005113639A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP05739541A EP1749043B1 (fr) 2004-05-07 2005-04-23 Copolycarbonates a fluidite amelioree
CN2005800224853A CN1980978B (zh) 2004-05-07 2005-04-23 具有更好流动能力的共聚碳酸酯
JP2007511934A JP2007536420A (ja) 2004-05-07 2005-04-23 流動性の改良されたコポリカーボネート

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102004022673.3 2004-05-07
DE102004022673A DE102004022673A1 (de) 2004-05-07 2004-05-07 Copolycarbonate mit verbesserter Fließfähigkeit

Publications (1)

Publication Number Publication Date
WO2005113639A1 true WO2005113639A1 (fr) 2005-12-01

Family

ID=34966912

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2005/004383 WO2005113639A1 (fr) 2004-05-07 2005-04-23 Copolycarbonates a fluidite amelioree

Country Status (9)

Country Link
US (1) US7425358B2 (fr)
EP (1) EP1749043B1 (fr)
JP (1) JP2007536420A (fr)
KR (1) KR20070012535A (fr)
CN (1) CN1980978B (fr)
DE (1) DE102004022673A1 (fr)
ES (1) ES2309751T3 (fr)
TW (1) TWI386432B (fr)
WO (1) WO2005113639A1 (fr)

Cited By (43)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011012294A1 (fr) 2009-07-29 2011-02-03 Bayer Materialscience Ag Produits multicouches contenant des revêtements à base d'acrylate
WO2011067282A1 (fr) 2009-12-05 2011-06-09 Bayer Materialscience Ag Compositions de polycarbonate dotées d'un dérivé triazinique à substitution phénolique
WO2012049091A1 (fr) 2010-10-12 2012-04-19 Bayer Materialscience Ag Absorbeurs d'uv spéciaux pour revêtements anti-uv durcissables
DE102010042939A1 (de) 2010-10-26 2012-04-26 Bayer Materialscience Aktiengesellschaft Fugenlose Heckklappe
WO2012059531A1 (fr) 2010-11-05 2012-05-10 Bayer Materialscience Ag Matières moulables en polycarbonate protégées contre les uv, dotées d'un retardateur de flamme et ayant un poids moléculaire à faible dégradation
WO2012059528A1 (fr) 2010-11-05 2012-05-10 Bayer Materialscience Ag Matières moulables en polycarbonate protégées contre les uv et ignifuges, ayant un poids moléculaire à faible dégradation
WO2012069590A1 (fr) 2010-11-24 2012-05-31 Bayer Materialscience Ag Procédé de fabrication de corps de forme optiques
WO2012080398A2 (fr) 2010-12-17 2012-06-21 Bayer Materialscience Ag Colorants organiques et compositions polymères colorées à grande stabilité aux intempéries
WO2013079478A1 (fr) 2011-11-30 2013-06-06 Bayer Intellectual Property Gmbh Corps multicouches en polycarbonate à effet brillant profond
WO2013079477A1 (fr) 2011-11-30 2013-06-06 Bayer Intellectual Property Gmbh Corps multicouches en polycarbonate à effet brillant profond
US8716374B2 (en) 2010-12-17 2014-05-06 Bayer Materialscience Ag Colour-stable LED substrates
WO2014095981A1 (fr) 2012-12-20 2014-06-26 Bayer Materialscience Ag Corps multicouche en polycarbonate doté d'une stabilité élevée aux intempéries
WO2014095967A1 (fr) 2012-12-20 2014-06-26 Bayer Materialscience Ag Colorants organiques et compositions polymères colorées présentant de bonnes propriétés de mise en œuvre
WO2014095954A1 (fr) 2012-12-20 2014-06-26 Bayer Materialscience Ag Masses de moulage de polycarbonate colorées de manière douce, contenant des pigments réfléchissant les ir
WO2014198739A1 (fr) 2013-06-14 2014-12-18 Bayer Materialscience Ag Feuille antireflet micro-structurée et à revêtement spécial
WO2014198751A1 (fr) 2013-06-14 2014-12-18 Bayer Materialscience Ag Agent de revêtement durcissable par rayonnement
WO2014206958A1 (fr) 2013-06-27 2014-12-31 Bayer Materialscience Ag Feuille metallisable, résistant aux rayures et aux solvants
US8968610B2 (en) 2010-12-17 2015-03-03 Bayer Materialscience Ag Polymer composition having heat-absorbing properties and high stability to weathering
US9029440B2 (en) 2010-12-17 2015-05-12 Bayer Materialscience Ag Polymer composition having heat-absorbing properties and high stability to weathering
US9713915B2 (en) 2013-01-18 2017-07-25 Covestro Deutschland Ag Bird protection glazing
WO2018060081A1 (fr) 2016-09-27 2018-04-05 Covestro Deutschland Ag Pare-brise de véhicule automobile
WO2018073111A1 (fr) 2016-10-18 2018-04-26 Covestro Deutschland Ag Procédé pour la fabrication d'un corps en matière synthétique qui convient comme élément décoratif
WO2018091558A1 (fr) 2016-11-17 2018-05-24 Covestro Deutschland Ag Corps multicouche opaque en polycarbonate pour la gestion de la chaleur
WO2018091556A1 (fr) 2016-11-17 2018-05-24 Covestro Deutschland Ag Corps multicouche transparent pour la gestion de la chaleur
WO2018108978A1 (fr) 2016-12-15 2018-06-21 Covestro Deutschland Ag Composant en polycarbonate revêtu transparent, sa fabrication et son utilisation
EP3395875A1 (fr) 2017-04-24 2018-10-31 Covestro Deutschland AG Matériau matriciel transparent au rayon laser pour applications de détection
WO2018202707A1 (fr) 2017-05-03 2018-11-08 Basf Se Agents de nucléation, procédés de production associés, et compositions polymères associées
WO2018206555A1 (fr) 2017-05-09 2018-11-15 Covestro Deutschland Ag Feuille plastique dotée d'une couche de colle durcissable aux uv et destinée à la protection d'un hologramme en composite de feuilles-photopolymère
WO2019121347A1 (fr) 2017-12-21 2019-06-27 Covestro Deutschland Ag Dispositif composé d'un corps multicouche et d'un capteur lidar
US10344170B2 (en) 2014-03-27 2019-07-09 Covestro Deutschland Ag Coating agent and films having increased mechanical and chemical resistance and sufficient deformability in 2-D film insert molding methods
WO2019192943A1 (fr) 2018-04-04 2019-10-10 Basf Se Utilisation d'une composition absorbant les rayonnements ultraviolets comme stabilisant lumière pour un article polymère artificiel façonné
WO2019228959A1 (fr) 2018-05-29 2019-12-05 Covestro Deutschland Ag Corps en polycarbonate multicouche opaque à haute résistance aux intempéries
WO2020182709A1 (fr) 2019-03-12 2020-09-17 Basf Se Articles polymères artificiels façonnés
WO2021094248A1 (fr) 2019-11-14 2021-05-20 Covestro Intellectual Property Gmbh & Co. Kg Composition thermoplastique destinée à un système de capteur lidar présentant des propriétés d'absorption améliorées
US11207871B2 (en) 2014-09-11 2021-12-28 Covestro Ag Bezel for motor vehicle glazing systems
WO2022037950A1 (fr) 2020-08-18 2022-02-24 Covestro Deutschland Ag Systèmes d'agents de revêtement, constitués d'un revêtement de base et d'un revêtement supérieur, et produit semi-fini à base de ceux-ci et production associée
US11267943B2 (en) 2017-05-09 2022-03-08 Covestro Deutschland Ag Film structure containing a photopolymer layer for holographic exposure and a coating layer of high resistance
WO2022148727A1 (fr) 2021-01-05 2022-07-14 Basf Se Stabilisation d'un article polymère mis en forme vis-à-vis de la dégradation induite par la lumière uv-c artificielle
US11640136B2 (en) 2017-05-09 2023-05-02 Covestro Deutschland Ag System consisting of two UV-curing dry-transfer coating layers for the protection of a hologram in a photopolymer film composite
WO2023141089A1 (fr) 2022-01-18 2023-07-27 Basf Se Articles polymères artificiels façonnés avec des particules d'oxyde métallique hybride
WO2023141091A1 (fr) 2022-01-18 2023-07-27 Basf Se Articles polymères artificiels façonnés avec particules d'oxyde métallique à cellules fermées
WO2024002735A1 (fr) 2022-06-29 2024-01-04 Basf Se Stabilisation d'un article polymère façonné vis-à-vis de la dégradation induite par la lumière uv-c artificielle
WO2024068415A1 (fr) 2022-09-29 2024-04-04 Basf Se Co-stabilisants pour polymères stabilisés par hydroxyphényle triazine

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102006025481A1 (de) * 2006-05-30 2007-12-06 Röhm Gmbh Verfahren zur Herstellung einer eingefärbten Folie aus thermoplastischem Kunststoffen, Folie und Verwendung der Folie
JP2007334054A (ja) * 2006-06-15 2007-12-27 Sharp Corp 電子写真感光体及びそれを用いた画像形成装置
DE102007022130B4 (de) * 2007-05-11 2015-02-19 Bayer Intellectual Property Gmbh Verfahren zur Herstellung von Polycarbonat nach dem Schmelzeumesterungsverfahren
US7642335B2 (en) * 2007-07-30 2010-01-05 Sabic Innovative Plastics Ip B.V. Polycarbonate with high refractive index
DE102008008842A1 (de) * 2008-02-13 2009-08-27 Bayer Materialscience Ag Alkylphenol zur Einstellung des Molekulargewichtes und Polycarbonatzusammensetzungen mit verbesserten Eigenschaften
DE102008019503A1 (de) * 2008-04-18 2009-10-22 Bayer Materialscience Ag Polycarbonate mit Umlagerungsstrukturen, cyclischen und linearen Oligomeren sowie verbessertem Fließverhalten
DE102008023800A1 (de) * 2008-05-15 2009-11-19 Bayer Materialscience Ag Alkylphenol zur Einstellung des Molekulargewichtes und Copolycarbonat mit verbesserten Eigenschaften
JP5740109B2 (ja) * 2010-07-20 2015-06-24 三菱瓦斯化学株式会社 ポリカーボネート樹脂及びそれを用いた積層成形部材
JP5731146B2 (ja) * 2010-08-31 2015-06-10 帝人株式会社 電子写真感光体バインダー用ポリカーボネート共重合体
JP5934228B2 (ja) * 2010-10-26 2016-06-15 トリンゼオ ヨーロッパ ゲゼルシャフト ミット ベシュレンクテル ハフツング 多層カーボネートシート
EP2862887B1 (fr) 2012-06-19 2016-12-14 Idemitsu Kosan Co., Ltd Copolymère de polycarbonate, liquide de revêtement l'utilisant et photorécepteur électrophotographique

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2701173A1 (de) * 1977-01-13 1978-07-20 Bayer Ag Verwendung von polycarbonaten fuer optische geraete
US4948871A (en) * 1987-09-28 1990-08-14 Asahi Kasei Kogyo Kabushiki Kaisha Method for producing a crystallized aromatic polycarbonate, and a crystallized aromatic polycarbonate obtained thereby
EP0402689A2 (fr) * 1989-06-10 1990-12-19 Bayer Ag Polycarbonats thermotropiques, procédé de leur préparation et leur usage pour la préparation des articles moulées, des filaments, des fibres et des feuilles
JPH083307A (ja) * 1994-06-24 1996-01-09 Mitsui Toatsu Chem Inc 芳香族ポリカーボネートの製造方法

Family Cites Families (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2237762A1 (de) * 1972-08-01 1974-02-14 Union Rheinische Braunkohlen Verfahren zur herstellung von dihydroxydiphenylaethern
JPS5377028A (en) 1976-12-17 1978-07-08 Teijin Ltd Aromatic diphenols and their preparation
JPS5778419A (en) * 1977-09-06 1982-05-17 Mobay Chemical Corp Copolycarbonate
JPS58142911A (ja) * 1982-02-22 1983-08-25 モベイ・ケミカル・コ−ポレ−シヨン コポリカ−ボネ−ト
DE3506845A1 (de) * 1985-02-27 1986-08-28 Röhm GmbH, 6100 Darmstadt Verfahren zur herstellung von 4,4'-dihydroxidiphenylether
DE3532881A1 (de) * 1985-09-14 1987-03-26 Hoechst Ag Verfahren zur herstellung von 4,4'-dihydroxydiphenylether
JPS63136051A (ja) 1986-11-28 1988-06-08 Canon Inc 電子写真感光体
JPH0198623A (ja) * 1987-10-13 1989-04-17 Idemitsu Petrochem Co Ltd ポリカーボネート及びその製造方法
JPH0794546B2 (ja) * 1987-09-28 1995-10-11 旭化成工業株式会社 芳香族ポリカーボネートの製造方法及びそれによって得られた結晶性芳香族ポリカーボネート粉体
US4847432A (en) * 1987-12-28 1989-07-11 General Electric Company Method for the purification of ion exchange resins used in the production of bisphenol A
NO170326C (no) * 1988-08-12 1992-10-07 Bayer Ag Dihydroksydifenylcykloalkaner
US5102975A (en) * 1990-04-12 1992-04-07 General Electric Company Liquid crystalline polycarbonate from dihydroxy biphenyl and dihydroxy diphenyl ether
US5976638A (en) * 1993-01-26 1999-11-02 Akzo Nobel Nv Optical recording medium comprising a homeotropically oriented liquid crystalline polymer film comprising dichroic dye
JPH0815533A (ja) * 1994-06-28 1996-01-19 Mitsubishi Rayon Co Ltd 近赤外透過型プラスチック光ファイバ
JP4093655B2 (ja) * 1998-10-22 2008-06-04 出光興産株式会社 ビスフェノールａの製造法
JP2002114841A (ja) * 2000-10-06 2002-04-16 Mitsui Chemicals Inc 光学部品
JP2002114842A (ja) * 2000-10-06 2002-04-16 Mitsui Chemicals Inc ポリカーボネート樹脂、及びそれを含んで構成される光学部品
JP2002167349A (ja) 2000-11-30 2002-06-11 Adchemco Corp ４，４’−ジヒドロキシジフェニルエーテルの製造方法
JP2003160526A (ja) 2001-11-27 2003-06-03 Manac Inc ヒドロキノンの二量体及び三量体の製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2701173A1 (de) * 1977-01-13 1978-07-20 Bayer Ag Verwendung von polycarbonaten fuer optische geraete
US4948871A (en) * 1987-09-28 1990-08-14 Asahi Kasei Kogyo Kabushiki Kaisha Method for producing a crystallized aromatic polycarbonate, and a crystallized aromatic polycarbonate obtained thereby
EP0402689A2 (fr) * 1989-06-10 1990-12-19 Bayer Ag Polycarbonats thermotropiques, procédé de leur préparation et leur usage pour la préparation des articles moulées, des filaments, des fibres et des feuilles
JPH083307A (ja) * 1994-06-24 1996-01-09 Mitsui Toatsu Chem Inc 芳香族ポリカーボネートの製造方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE CA [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; TOTANI, YOSHUKI ET AL: "Manufacture of aromatic polycarbonates in halogen-free solvents", XP002337120, retrieved from STN Database accession no. 124:262048 *
FACTOR A., LYNCH J.C., GREENBERG F.H.: "The Synthesis, Characterization, and Weathering Behavior of Polycarbonates derived from 3,3'-Dihydroxydiphenyl Ether", JOURNAL OF POLYMER SCIENCE: PART A: POLYMER CHEMISTRY, vol. 25, 1987, pages 3413 - 3422, XP002335610 *

Cited By (61)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011012294A1 (fr) 2009-07-29 2011-02-03 Bayer Materialscience Ag Produits multicouches contenant des revêtements à base d'acrylate
US8932684B2 (en) 2009-07-29 2015-01-13 Bayer Materialscience Ag Multi-layer products comprising acrylate containing coatings
US8741992B2 (en) 2009-12-05 2014-06-03 Bayer Intellectual Property Gmbh Polycarbonate compositions with phenolically substituted triazine derivative
WO2011067282A1 (fr) 2009-12-05 2011-06-09 Bayer Materialscience Ag Compositions de polycarbonate dotées d'un dérivé triazinique à substitution phénolique
WO2012049091A1 (fr) 2010-10-12 2012-04-19 Bayer Materialscience Ag Absorbeurs d'uv spéciaux pour revêtements anti-uv durcissables
EP2447236A1 (fr) 2010-10-12 2012-05-02 Bayer MaterialScience AG Absorbeur à UV spécifique pour revêtements de protection contre les UV durcissables
US9273213B2 (en) 2010-10-12 2016-03-01 Covestro Deutschland Ag Special UV absorbers for curable UV-protective coatings
DE102010042939A1 (de) 2010-10-26 2012-04-26 Bayer Materialscience Aktiengesellschaft Fugenlose Heckklappe
WO2012055873A2 (fr) 2010-10-26 2012-05-03 Bayer Materialscience Ag Hayon sans joints
WO2012059531A1 (fr) 2010-11-05 2012-05-10 Bayer Materialscience Ag Matières moulables en polycarbonate protégées contre les uv, dotées d'un retardateur de flamme et ayant un poids moléculaire à faible dégradation
WO2012059528A1 (fr) 2010-11-05 2012-05-10 Bayer Materialscience Ag Matières moulables en polycarbonate protégées contre les uv et ignifuges, ayant un poids moléculaire à faible dégradation
US9193848B2 (en) 2010-11-05 2015-11-24 Bayer Intellectual Property Gmbh Flame-resistant, UV-protected polycarbonate moulding compositions of low molecular weight degradation
WO2012069590A1 (fr) 2010-11-24 2012-05-31 Bayer Materialscience Ag Procédé de fabrication de corps de forme optiques
US8641784B2 (en) 2010-12-17 2014-02-04 Bayer Materialscience Ag Organic colouring agents and coloured polymer compositions with a high stability to weathering
US8716374B2 (en) 2010-12-17 2014-05-06 Bayer Materialscience Ag Colour-stable LED substrates
WO2012080398A2 (fr) 2010-12-17 2012-06-21 Bayer Materialscience Ag Colorants organiques et compositions polymères colorées à grande stabilité aux intempéries
US9212272B2 (en) 2010-12-17 2015-12-15 Bayer Materialscience Ag Organic colouring agents and coloured polymer compositions with a high stability to weathering
US9029440B2 (en) 2010-12-17 2015-05-12 Bayer Materialscience Ag Polymer composition having heat-absorbing properties and high stability to weathering
US8968610B2 (en) 2010-12-17 2015-03-03 Bayer Materialscience Ag Polymer composition having heat-absorbing properties and high stability to weathering
WO2013079477A1 (fr) 2011-11-30 2013-06-06 Bayer Intellectual Property Gmbh Corps multicouches en polycarbonate à effet brillant profond
WO2013079478A1 (fr) 2011-11-30 2013-06-06 Bayer Intellectual Property Gmbh Corps multicouches en polycarbonate à effet brillant profond
US9845412B2 (en) 2012-12-20 2017-12-19 Covestro Deutschland Ag Multi-layer body made of polycarbonate with high weathering resistance
WO2014095954A1 (fr) 2012-12-20 2014-06-26 Bayer Materialscience Ag Masses de moulage de polycarbonate colorées de manière douce, contenant des pigments réfléchissant les ir
WO2014095967A1 (fr) 2012-12-20 2014-06-26 Bayer Materialscience Ag Colorants organiques et compositions polymères colorées présentant de bonnes propriétés de mise en œuvre
WO2014095981A1 (fr) 2012-12-20 2014-06-26 Bayer Materialscience Ag Corps multicouche en polycarbonate doté d'une stabilité élevée aux intempéries
US9713915B2 (en) 2013-01-18 2017-07-25 Covestro Deutschland Ag Bird protection glazing
WO2014198751A1 (fr) 2013-06-14 2014-12-18 Bayer Materialscience Ag Agent de revêtement durcissable par rayonnement
WO2014198739A1 (fr) 2013-06-14 2014-12-18 Bayer Materialscience Ag Feuille antireflet micro-structurée et à revêtement spécial
WO2014206958A1 (fr) 2013-06-27 2014-12-31 Bayer Materialscience Ag Feuille metallisable, résistant aux rayures et aux solvants
US10526504B2 (en) 2013-06-27 2020-01-07 Covestro Deutschland Ag Metallizable, scratch-resistant and solvent-resistant film
US10000658B2 (en) 2013-06-27 2018-06-19 Covestro Deutschland Ag Metallizable, scratch-resistant and solvent-resistant film
US10344170B2 (en) 2014-03-27 2019-07-09 Covestro Deutschland Ag Coating agent and films having increased mechanical and chemical resistance and sufficient deformability in 2-D film insert molding methods
US11207871B2 (en) 2014-09-11 2021-12-28 Covestro Ag Bezel for motor vehicle glazing systems
WO2018060081A1 (fr) 2016-09-27 2018-04-05 Covestro Deutschland Ag Pare-brise de véhicule automobile
WO2018073111A1 (fr) 2016-10-18 2018-04-26 Covestro Deutschland Ag Procédé pour la fabrication d'un corps en matière synthétique qui convient comme élément décoratif
US11440382B2 (en) 2016-11-17 2022-09-13 Covestro Deutschland Ag Transparent multilayer structure for thermal management
WO2018091558A1 (fr) 2016-11-17 2018-05-24 Covestro Deutschland Ag Corps multicouche opaque en polycarbonate pour la gestion de la chaleur
US11351764B2 (en) 2016-11-17 2022-06-07 Covestro Deutschland Ag Opaque multi-layer body of polycarbonate for heat management
WO2018091556A1 (fr) 2016-11-17 2018-05-24 Covestro Deutschland Ag Corps multicouche transparent pour la gestion de la chaleur
US11027312B2 (en) 2016-12-15 2021-06-08 Covestro Deutschland Ag Transparently coated polycarbonate component, its production and use
WO2018108978A1 (fr) 2016-12-15 2018-06-21 Covestro Deutschland Ag Composant en polycarbonate revêtu transparent, sa fabrication et son utilisation
US11512181B2 (en) 2017-04-24 2022-11-29 Covestro Deutschland Ag Laser beam-permeable substrate material for use on sensors
EP3395875A1 (fr) 2017-04-24 2018-10-31 Covestro Deutschland AG Matériau matriciel transparent au rayon laser pour applications de détection
WO2018197398A1 (fr) 2017-04-24 2018-11-01 Covestro Deutschland Ag Matériau de substrat perméable aux faisceaux lasers pour applications de détection
WO2018202707A1 (fr) 2017-05-03 2018-11-08 Basf Se Agents de nucléation, procédés de production associés, et compositions polymères associées
US11414531B2 (en) 2017-05-03 2022-08-16 Basf Se Nucleating agents, methods for their production, and associated polymer compositions
WO2018206555A1 (fr) 2017-05-09 2018-11-15 Covestro Deutschland Ag Feuille plastique dotée d'une couche de colle durcissable aux uv et destinée à la protection d'un hologramme en composite de feuilles-photopolymère
US11640136B2 (en) 2017-05-09 2023-05-02 Covestro Deutschland Ag System consisting of two UV-curing dry-transfer coating layers for the protection of a hologram in a photopolymer film composite
US11267943B2 (en) 2017-05-09 2022-03-08 Covestro Deutschland Ag Film structure containing a photopolymer layer for holographic exposure and a coating layer of high resistance
WO2019121347A1 (fr) 2017-12-21 2019-06-27 Covestro Deutschland Ag Dispositif composé d'un corps multicouche et d'un capteur lidar
US11747447B2 (en) 2017-12-21 2023-09-05 Covestro Deutschland Ag Device comprising a multi-layer body and a LiDAR sensor
WO2019192943A1 (fr) 2018-04-04 2019-10-10 Basf Se Utilisation d'une composition absorbant les rayonnements ultraviolets comme stabilisant lumière pour un article polymère artificiel façonné
WO2019228959A1 (fr) 2018-05-29 2019-12-05 Covestro Deutschland Ag Corps en polycarbonate multicouche opaque à haute résistance aux intempéries
WO2020182709A1 (fr) 2019-03-12 2020-09-17 Basf Se Articles polymères artificiels façonnés
WO2021094248A1 (fr) 2019-11-14 2021-05-20 Covestro Intellectual Property Gmbh & Co. Kg Composition thermoplastique destinée à un système de capteur lidar présentant des propriétés d'absorption améliorées
WO2022037950A1 (fr) 2020-08-18 2022-02-24 Covestro Deutschland Ag Systèmes d'agents de revêtement, constitués d'un revêtement de base et d'un revêtement supérieur, et produit semi-fini à base de ceux-ci et production associée
WO2022148727A1 (fr) 2021-01-05 2022-07-14 Basf Se Stabilisation d'un article polymère mis en forme vis-à-vis de la dégradation induite par la lumière uv-c artificielle
WO2023141089A1 (fr) 2022-01-18 2023-07-27 Basf Se Articles polymères artificiels façonnés avec des particules d'oxyde métallique hybride
WO2023141091A1 (fr) 2022-01-18 2023-07-27 Basf Se Articles polymères artificiels façonnés avec particules d'oxyde métallique à cellules fermées
WO2024002735A1 (fr) 2022-06-29 2024-01-04 Basf Se Stabilisation d'un article polymère façonné vis-à-vis de la dégradation induite par la lumière uv-c artificielle
WO2024068415A1 (fr) 2022-09-29 2024-04-04 Basf Se Co-stabilisants pour polymères stabilisés par hydroxyphényle triazine

Also Published As

Publication number Publication date
US7425358B2 (en) 2008-09-16
DE102004022673A1 (de) 2005-11-24
EP1749043A1 (fr) 2007-02-07
CN1980978A (zh) 2007-06-13
ES2309751T3 (es) 2008-12-16
US20050250915A1 (en) 2005-11-10
KR20070012535A (ko) 2007-01-25
JP2007536420A (ja) 2007-12-13
TW200617060A (en) 2006-06-01
EP1749043B1 (fr) 2008-07-30
CN1980978B (zh) 2012-04-25
TWI386432B (zh) 2013-02-21

Similar Documents

Publication Publication Date Title
EP1749043B1 (fr) Copolycarbonates a fluidite amelioree
EP2081974B1 (fr) Polycarbonates et copolycarbonates a adherence amelioree sur les metaux
EP2336245A1 (fr) Compositions de polycarbonate dotées d'une dureté de surface améliorée
EP1613682B1 (fr) Polycarbonates et copolycarbonates ultra-ramifies presentant un meilleur facteur d'ecoulement, fabrication et utilisation
EP1359176B1 (fr) Polycarbonates, polyestercarbonates et polyesters ayant des groupes terminaux spécifiques
DE102008036406A1 (de) Modifizierte Polycarbonate mit verbesserten Oberflächeneigenschaften
EP1655324B1 (fr) Polycarbonate ramifié
WO2010105769A1 (fr) Copolycarbonates ayant des propriétés améliorées
EP1266924B1 (fr) Polycarbonates et polyestercarbonates ayant des groupes terminaux rétifiés
EP1421072A1 (fr) Polycarbonates de polyester obtenus a partir de diphenols particuliers
EP1556434B1 (fr) Polycarbonates, polyestercarbonates et polyesters contenant des phenols substitues par un cycloalkyle et lateraux
EP1587852A1 (fr) Polycarbonates et copolycarbonates cycliques, leur production et leur utilisation
EP1660425A1 (fr) Polycarbonates et copolycarbonates ayant une absorption d'eau reduite et une aptitude a l'ecoulement amelioree, leur production et leur utilisation
WO2010060549A1 (fr) Copolycarbonates à dureté de surface améliorée

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KM KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SM SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LT LU MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 2005739541

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 2007511934

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE

WWW Wipo information: withdrawn in national office

Country of ref document: DE

WWE Wipo information: entry into national phase

Ref document number: 1020067025648

Country of ref document: KR

WWE Wipo information: entry into national phase

Ref document number: 200580022485.3

Country of ref document: CN

WWP Wipo information: published in national office

Ref document number: 1020067025648

Country of ref document: KR

WWP Wipo information: published in national office

Ref document number: 2005739541

Country of ref document: EP

WWG Wipo information: grant in national office

Ref document number: 2005739541

Country of ref document: EP